CN113105616A - Preparation method of hydrophobic polyether polyol - Google Patents

Abstract

The invention belongs to the technical field of polyether polyol, and particularly relates to a preparation method of hydrophobic polyether polyol. The preparation method of the hydrophobic polyether polyol comprises the steps of adopting a hydrophobic initiator as an initiator, taking alkali metal or DMC as a catalyst, carrying out polymerization reaction with a hydrophobic polymerization monomer under the pressure of-0.1 to-0.4 MPa and the temperature of 80-180 ℃ to obtain a polyether polyol crude polymer, and refining to obtain the hydrophobic polyether polyol; the hydrophobic initiator is one or more of hydroxyl-terminated aliphatic diol, bisphenol A, bisphenol F and hydroxyl-terminated polysiloxane; the hydrophobic polymerization monomer is one or a mixture of propylene oxide and butylene oxide and 1, 2-epoxypentane. According to the invention, the hydrophobic polymerization monomer and the hydrophobic initiator are adopted for polymerization to prepare the hydrophobic polyether polyol, and the prepared hydrophobic polyether polyol is used in the polyurethane material, so that the hydrophobic property of the polyurethane material is greatly improved.

Description

Preparation method of hydrophobic polyether polyol

Technical Field

The invention belongs to the technical field of polyether polyol, and particularly relates to a preparation method of hydrophobic polyether polyol.

Background

The hydrophobic material has excellent water repellency and self-cleaning property, and has wide application in the fields of building water repellency, soil resistance, anti-icing, high-end clothing waterproof coating, metal corrosion resistance, oil-water separation and the like. Polyurethane hydrophobic materials are a more widely used type of hydrophobic material. Hydrophobic polyether polyols are important starting materials for the synthesis of hydrophobic polyurethane materials.

In the prior art, hydrophobic monomers are generally adopted for polymerization, so as to obtain hydrophobic polyether polyol. For example, patent CN2020108982992 discloses a method for preparing low-unsaturation random copolymerization hydrophobic polyether polyol, wherein an initiator and alkylene oxide are polymerized under the action of a double metal cyanide complex catalyst and an acid as an auxiliary agent to obtain the low-unsaturation random copolymerization hydrophobic polyether polyol, wherein the alkylene oxide comprises propylene oxide and butylene oxide. The hydrophobic polyether polyol obtained by randomly copolymerizing low-unsaturation degree and having low unsaturation degree and excellent hydrophobic effect is prepared by polymerizing monomers of propylene oxide and butylene oxide through hydrophobicity. However, the hydrophobicity of polyether polyol obtained by the preparation method needs to be further improved.

Disclosure of Invention

The invention solves the technical problem of providing a preparation method of hydrophobic polyether polyol, which adopts hydrophobic polymerization monomers and hydrophobic initiator for polymerization, and the prepared hydrophobic polyether polyol is used in polyurethane materials, thereby greatly improving the hydrophobic performance of the polyurethane materials on the basis of not influencing other performances of the polyurethane materials.

The preparation method of the hydrophobic polyether polyol comprises the following steps:

(1) adopting a hydrophobic initiator as an initiator, and alkali metal or DMC as a catalyst, and carrying out polymerization reaction with a hydrophobic polymerization monomer under the pressure of-0.1 to-0.4 MPa and the temperature of 80 to 180 ℃ to prepare a polyether polyol crude polymer;

(2) and (2) refining the polyether polyol crude polymer prepared in the step (1) to obtain the hydrophobic polyether polyol.

In the step (1), the hydrophobic initiator is one or more of hydroxyl-terminated aliphatic diol, bisphenol A, bisphenol F and hydroxyl-terminated polysiloxane.

Wherein the structural formula of the hydroxyl-terminated aliphatic diol is HO- (CH)₂)_n-OH, wherein n.gtoreq.6.

In the step (1), the hydrophobic polymerization monomer is a mixture of propylene oxide and one or two of butylene oxide and 1, 2-epoxypentane, wherein the addition amount of the propylene oxide accounts for 5% -90% of the total content of the alkylene oxide.

In the step (1), the mass ratio of the initiator to the hydrophobic polymerization monomer is 0.05-1: 1.

In the step (1), the alkali metal catalyst is one of potassium hydroxide, sodium hydroxide, cesium hydroxide, potassium methoxide and sodium methoxide.

In the step (1), the dosage of the catalyst is 0.1-0.8% of the total mass of the hydrophobic initiator and the hydrophobic polymerization monomer.

In the step (1), the polymerization mode of the initiator and the hydrophobic polymerization monomer is one of the following modes:

mode 1: initiator + propylene oxide + butylene oxide;

mode 2: a mixture of initiator + propylene oxide and butylene oxide;

mode 3: a mixture of initiator +1, 2-epoxypentane and propylene oxide;

mode 4: a mixture of initiator + propylene oxide, butylene oxide and 1, 2-epoxypentane;

mode 5: a mixture of initiator + propylene oxide + butylene oxide and propylene oxide;

mode 6: initiator + propylene oxide +1, 2-epoxypentane;

mode 7: a mixture of initiator + propylene oxide + butylene oxide and 1, 2-epoxypentane;

mode 8: initiator + mixture of propylene oxide and butylene oxide + mixture of propylene oxide and 1, 2-epoxypentane.

Specifically, the polymerization mode of the initiator and the hydrophobic polymerization monomer is one of the following modes:

mode 1: the initiator is polymerized with propylene oxide and then with butylene oxide.

Mode 2: the initiator is polymerized with a mixture of propylene oxide and butylene oxide.

Mode 3: the initiator is polymerized with a mixture of 1, 2-epoxypentane and propylene oxide.

Mode 4: the initiator is polymerized first with propylene oxide and then with a mixture of propylene oxide and ethylene oxide.

Mode 5: the initiator is polymerized with propylene oxide and then with a mixture of butylene oxide and propylene oxide.

Mode 6: the initiator is polymerized with propylene oxide and then with 1, 2-epoxypentane.

Mode 7: the initiator is polymerized first with propylene oxide and then with a mixture of butylene oxide and 1, 2-epoxypentane.

Mode 8: the initiator is polymerized first with a mixture of butylene oxide and propylene oxide and then with a mixture of propylene oxide and 1, 2-epoxypentane.

In the step (2), the refining treatment comprises neutralization, adsorption, crystallization and filtration.

The hydrophobic polyether polyol prepared by the invention has the number average molecular weight of 1000-10000g/mol and the functionality of 2.

Compared with the prior art, the invention has the following beneficial effects:

according to the invention, the hydrophobic polymerization monomer and the hydrophobic initiator are adopted for polymerization to prepare the hydrophobic polyether polyol, the hydrophobic property of the polyether polyol is greatly improved by improving the content of hydrophobic groups in the polyether polyol structure, and the prepared hydrophobic polyether polyol is used in a polyurethane material, so that the hydrophobic property of the polyurethane material is greatly improved on the basis of not influencing other properties of the polyurethane material, and the hydrophobic polyether polyol can be used in the fields of building waterproof materials, high-grade clothing finishing, oil-water separation and the like.

Drawings

FIG. 1 is a surface contact angle test chart of a polyurethane coating film prepared from a polyether polyol of example 1 of the present invention;

FIG. 2 is a surface contact angle test chart of a polyurethane coating film prepared from a polyether polyol of example 2 of the present invention;

FIG. 3 is a surface contact angle test chart of a polyurethane coating film prepared from a polyether polyol of example 3 of the present invention;

FIG. 4 is a surface contact angle test chart of a polyurethane coating film prepared from the polyether polyol of comparative example 1 of the present invention;

FIG. 5 is a surface contact angle test chart of a polyurethane coating film prepared from the polyether polyol of comparative example 2 of the present invention;

FIG. 6 is a surface contact angle test chart of a polyurethane coating film prepared from the polyether polyol of comparative example 3 of the present invention.

Detailed Description

The present invention is further described below with reference to examples. The following are merely exemplary embodiments of the present invention and should not be construed as limiting the scope of the embodiments of the present invention.

Example 1

284.85g of bisphenol A and 7.50g of solid potassium hydroxide catalyst are added into a 5L stainless steel reaction kettle, nitrogen gas is replaced, and the oxygen content in the reaction kettle is measured to be lower than 80 ppm; heating the reaction kettle to 105 ℃, carrying out nitrogen bubbling and reduced pressure dehydration, keeping the temperature in the kettle at 110 +/-2 ℃ and the pressure at 0.2 +/-0.2 MPa, continuously adding 1772.12g of propylene oxide and 443.03g of butylene oxide, then carrying out internal pressure reaction for 30 minutes, removing unreacted polymerization monomers, cooling and discharging to obtain a hydrophobic polyether polyol crude polymer; and neutralizing, adsorbing, crystallizing, filtering and refining the polyether polyol crude polymer to obtain the hydrophobic polyether polyol.

The number average molecular weight of the product was 2000g/mol, functionality 2.

Example 2

951.21g of bisphenol A and 7.50g of solid potassium hydroxide catalyst are added into a 5L stainless steel reaction kettle, nitrogen gas is replaced, and the oxygen content in the reaction kettle is measured to be lower than 80 ppm; heating the reaction kettle to 105 ℃, carrying out nitrogen bubbling and reduced pressure dehydration, keeping the temperature in the kettle at 110 +/-2 ℃ and the pressure at 0.2 +/-0.2 MPa, continuously adding 1548.79g of propylene oxide, carrying out internal pressure reaction, and removing unreacted propylene oxide; and neutralizing, adsorbing, crystallizing, filtering and refining the polyether polyol crude polymer to obtain the oligomer.

748.66g of oligomer is added into a 5L stainless steel reaction kettle, 0.007g of sulfuric acid and 0.08g of DMC catalyst are added, the mixture of 1488.64g of propylene oxide and 262.7g of butylene oxide is continuously added under the conditions of 120 ℃ reduced pressure dehydration for 2h and 140 ℃, after the addition of the polymerization monomer, internal pressure reaction is carried out, and the unreacted polymerization monomer is removed, thus obtaining the hydrophobic polyether polyol.

The number average molecular weight of the product was 2000g/mol, functionality 2.

Example 3

147.45g of 1, 6-hexanediol and 7.50g of solid potassium hydroxide catalyst are added into a 5L stainless steel reaction kettle, nitrogen gas is replaced, and the oxygen content in the reaction kettle is measured to be lower than 80 ppm; heating the reaction kettle to 105 ℃, carrying out nitrogen bubbling and reduced pressure dehydration, keeping the temperature in the kettle at 110 +/-2 ℃ and the pressure at 0.2 +/-0.2 MPa, continuously adding 1999.67g of propylene oxide and 352.88g of butylene oxide, then carrying out internal pressure reaction for 30 minutes, removing unreacted polymerization monomers, cooling and discharging to obtain a hydrophobic polyether polyol crude polymer; and neutralizing, adsorbing, crystallizing, filtering and refining the polyether polyol crude polymer to obtain the hydrophobic polyether polyol.

The number average molecular weight of the product was 2000g/mol, functionality 2.

Example 4

350g of hexanediol and 3.55g of potassium methoxide catalyst are added into a 5L stainless steel reaction kettle, nitrogen is replaced, and the oxygen content in the reaction kettle is measured to be lower than 80 ppm; heating the reaction kettle to 105 ℃, carrying out nitrogen bubbling and reduced pressure dehydration, keeping the temperature in the kettle at 110 +/-2 ℃ and the pressure at 0.2 +/-0.2 MPa, continuously adding 834.73g of propylene oxide, then carrying out internal pressure reaction for 30 minutes, removing unreacted polymerized monomers, cooling and discharging to obtain oligomers;

adding 800g of oligomer into a 5L stainless steel reaction kettle, adding 0.007g of sulfuric acid and 0.08g of DMC catalyst, carrying out vacuum dehydration at 120 ℃ for 2h, continuously adding a mixture of 800g of propylene oxide, 300g of butylene oxide and 100g of 1, 2-epoxypentane at 140 ℃, carrying out internal pressure reaction after the addition of the polymerization monomer is finished, and removing the unreacted polymerization monomer to obtain the hydrophobic polyether polyol.

The number average molecular weight of the product was 1000g/mol, functionality 2.

Example 5

Adding 350g of bisphenol F and 5.24g of solid sodium methoxide catalyst into a 5L stainless steel reaction kettle, replacing with nitrogen, and measuring the oxygen content in the reaction kettle to be lower than 80 ppm; heating the reaction kettle to 105 ℃, carrying out nitrogen bubbling and reduced pressure dehydration, keeping the temperature in the kettle at 110 +/-2 ℃ and the pressure at 0.2 +/-0.2 MPa, continuously adding 1397.90g of propylene oxide, then carrying out internal pressure reaction for 30 minutes, removing unreacted polymerized monomers, cooling and discharging to obtain oligomers;

adding 800g of oligomer into a 5L stainless steel reaction kettle, adding 0.007g of sulfuric acid and 0.08g of DMC catalyst, carrying out vacuum dehydration at 120 ℃ for 2h, continuously adding a mixture of 2451.0g of propylene oxide and 735.30g of 1, 2-epoxypentane at 140 ℃, carrying out internal pressure reaction after adding a polymerization monomer, and removing unreacted polymerization monomer to obtain the hydrophobic polyether polyol.

The number average molecular weight of the product was 8000g/mol, functionality 2.

Comparative example 1

Polyether polyol DL-2000D, functionality of 2, molecular weight of 2000g/mol, produced by Shandong Lanxingdao Co., Ltd.

Comparative example 2

150g of 1, 2-propylene glycol and 11.83g of solid potassium hydroxide catalyst are added into a 5L stainless steel reaction kettle, nitrogen is replaced, and the oxygen content in the reaction kettle is measured to be lower than 80 ppm; heating the reaction kettle to 105 ℃, carrying out nitrogen bubbling and reduced pressure dehydration, keeping the temperature in the kettle at 110 +/-2 ℃ and the pressure at 0.2 +/-0.2 MPa, continuously adding 3034.16g of propylene oxide and 758.54g of butylene oxide, then carrying out internal pressure reaction for 30 minutes, removing unreacted polymerization monomers, cooling and discharging to obtain a hydrophobic polyether polyol crude polymer; and neutralizing, adsorbing, crystallizing, filtering and refining the polyether polyol crude polymer to obtain the hydrophobic polyether polyol.

The number average molecular weight of the product was 2000g/mol, functionality 2.

Comparative example 3

284.85g of bisphenol A and 7.50g of solid potassium hydroxide catalyst are added into a 5L stainless steel reaction kettle, nitrogen gas is replaced, and the oxygen content in the reaction kettle is measured to be lower than 80 ppm; heating the reaction kettle to 105 ℃, carrying out nitrogen bubbling and reduced pressure dehydration, keeping the temperature in the kettle at 110 +/-2 ℃ and the pressure at 0.2 +/-0.2 MPa, continuously adding 1772.12g of propylene oxide and 443.03g of ethylene oxide, then carrying out internal pressure reaction for 30 minutes, removing unreacted polymerization monomers, cooling and discharging to obtain a hydrophobic polyether polyol crude polymer; and neutralizing, adsorbing, crystallizing, filtering and refining the polyether polyol crude polymer to obtain the hydrophobic polyether polyol.

The number average molecular weight of the product was 2000g/mol, functionality 2.

The polyether polyols of examples 1 to 3 and comparative examples 1 to 3 were tested for their indices and the results are shown in Table 1.

TABLE 1 polyether polyol indicator test results

Further, the polyether polyols of examples 1 to 3 and comparative examples 1 to 3 were used as the polyether polyol raw materials of the B component, respectively, to prepare polyurethane coating films, and the hydrophobic properties and other properties of the polyurethane coating films were tested, respectively.

The polyurethane coating formula is as follows:

the component A comprises: 5.27g of 1, 4-butanediol, 5g of a plasticizer (dioctyl phthalate), 0.02g of a defoaming agent (DF-8205, Defeng defoaming agent Co., Ltd., Dongguan) and 0.01g of a catalyst (Dabcot-12, gas Co., Ltd.);

and B component: 200g of polyether polyol, MDI-5095.33 g, xylene 25g, and catalyst (Dabcot-12, USA gas Co.) 0.05 g.

The preparation method of the polyurethane coating film comprises the following steps:

(1) the component A comprises: uniformly mixing the raw materials of the component A according to the formula, and packaging for later use;

(2) and B component: adding 200g of polyether polyol and 25g of xylene into a reactor, heating to 50 ℃, adding MDI-50, stirring for 10min, heating to 70 ℃, adding a catalyst, reacting for 30min, measuring NCO%, and finishing the reaction when the NCO% content reaches 7.4%; cooling to 30 ℃, defoaming by regulating and controlling the stirring rotating speed and the vacuum degree, and then packaging for later use;

(3) a, B components are evenly stirred according to the mass ratio of 100:10.3, then are coated on glass in a scraping way, and the film is formed after curing for seven days.

The contact angle of the water on the surface of the cured adhesive film was measured by a contact angle measuring instrument, and the measurement results are shown in table 2. And testing the mechanical property of the prepared coating film according to GB/T528-2009.

TABLE 2 polyurethane coating film Performance test results

As can be seen from Table 2, the water contact angle of the polyurethane adhesive film prepared by the hydrophobic polyether polyol is not less than 120 degrees, which is obviously higher than that of the comparative examples 1-3, and the adhesive film prepared by the hydrophobic polyether polyol has very excellent hydrophobic function, and the polyurethane adhesive film prepared by the hydrophobic polyether polyol has excellent mechanical properties.

Claims (9)

1. A method for preparing hydrophobic polyether polyol is characterized in that: the method comprises the following steps:

(1) adopting a hydrophobic initiator as an initiator, and alkali metal or DMC as a catalyst, and carrying out polymerization reaction with a hydrophobic polymerization monomer under the pressure of-0.1 to-0.4 MPa and the temperature of 80 to 180 ℃ to prepare a polyether polyol crude polymer;

(2) refining the polyether polyol crude polymer prepared in the step (1) to obtain hydrophobic polyether polyol;

wherein the hydrophobic initiator is one or more of hydroxyl-terminated aliphatic diol, bisphenol A, bisphenol F and hydroxyl-terminated polysiloxane;

the hydrophobic polymerization monomer is a mixture of propylene oxide and one or two of butylene oxide and 1, 2-epoxypentane, wherein the addition amount of the propylene oxide accounts for 5-90% of the total content of the alkylene oxide.

2. The process for the preparation of a hydrophobic polyether polyol according to claim 1, characterized in that: the structural formula of the hydroxyl-terminated aliphatic diol is HO- (CH)₂)_n-OH, wherein n.gtoreq.6.

3. The process for the preparation of a hydrophobic polyether polyol according to claim 1, characterized in that: in the step (1), the mass ratio of the initiator to the hydrophobic polymerization monomer is 0.05-1: 1.

4. The process for the preparation of a hydrophobic polyether polyol according to claim 1, characterized in that: in the step (1), the alkali metal catalyst is one of potassium hydroxide, sodium hydroxide, cesium hydroxide, potassium methoxide and sodium methoxide.

5. The process for the preparation of a hydrophobic polyether polyol according to claim 1, characterized in that: in the step (1), the dosage of the catalyst is 0.1-0.8% of the total mass of the hydrophobic initiator and the hydrophobic polymerization monomer.

6. The process for the preparation of a hydrophobic polyether polyol according to claim 1, characterized in that: in the step (1), the polymerization mode of the initiator and the hydrophobic polymerization monomer is one of the following modes:

mode 1: initiator + propylene oxide + butylene oxide;

mode 2: a mixture of initiator + propylene oxide and butylene oxide;

mode 3: a mixture of initiator +1, 2-epoxypentane and propylene oxide;

mode 4: a mixture of initiator + propylene oxide, butylene oxide and 1, 2-epoxypentane;

mode 5: a mixture of initiator + propylene oxide + butylene oxide and propylene oxide;

mode 6: initiator + propylene oxide +1, 2-epoxypentane;

mode 7: a mixture of initiator + propylene oxide + butylene oxide and 1, 2-epoxypentane;

mode 8: initiator + mixture of propylene oxide and butylene oxide + mixture of propylene oxide and 1, 2-epoxypentane.

7. The process for the preparation of a hydrophobic polyether polyol according to claim 1, characterized in that: the polymerization mode of the initiator and the hydrophobic polymerization monomer is one of the following modes:

mode 1: the initiator is polymerized with propylene oxide and then with butylene oxide.

Mode 2: the initiator is polymerized with a mixture of propylene oxide and butylene oxide.

Mode 3: the initiator is polymerized with a mixture of 1, 2-epoxypentane and propylene oxide.

Mode 4: the initiator is polymerized first with propylene oxide and then with a mixture of propylene oxide and ethylene oxide.

Mode 5: the initiator is polymerized with propylene oxide and then with a mixture of butylene oxide and propylene oxide.

Mode 6: the initiator is polymerized with propylene oxide and then with 1, 2-epoxypentane.

Mode 7: the initiator is polymerized first with propylene oxide and then with a mixture of butylene oxide and 1, 2-epoxypentane.

Mode 8: the initiator is polymerized first with a mixture of butylene oxide and propylene oxide and then with a mixture of propylene oxide and 1, 2-epoxypentane.

8. The process for the preparation of a hydrophobic polyether polyol according to claim 1, characterized in that: in the step (2), the refining treatment comprises neutralization, adsorption, crystallization and filtration.

9. The process for the preparation of a hydrophobic polyether polyol according to claim 1, characterized in that: in the step (2), the prepared hydrophobic polyether polyol has the number average molecular weight of 1000-10000g/mol and the functionality of 2.

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